JP5138401B2 - Optical glass, glass gob for press molding, optical element, manufacturing method thereof, and manufacturing method of optical element blank - Google Patents
Optical glass, glass gob for press molding, optical element, manufacturing method thereof, and manufacturing method of optical element blank Download PDFInfo
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- JP5138401B2 JP5138401B2 JP2008019422A JP2008019422A JP5138401B2 JP 5138401 B2 JP5138401 B2 JP 5138401B2 JP 2008019422 A JP2008019422 A JP 2008019422A JP 2008019422 A JP2008019422 A JP 2008019422A JP 5138401 B2 JP5138401 B2 JP 5138401B2
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B17/00—Forming molten glass by flowing-out, pushing-out, extruding or drawing downwardly or laterally from forming slits or by overflowing over lips
- C03B17/06—Forming glass sheets
- C03B17/061—Forming glass sheets by lateral drawing or extrusion
- C03B17/062—Forming glass sheets by lateral drawing or extrusion combined with flowing onto a solid or gaseous support from which the sheet is drawn
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B40/00—Preventing adhesion between glass and glass or between glass and the means used to shape it, hold it or support it
- C03B40/02—Preventing adhesion between glass and glass or between glass and the means used to shape it, hold it or support it by lubrication; Use of materials as release or lubricating compositions
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B40/00—Preventing adhesion between glass and glass or between glass and the means used to shape it, hold it or support it
- C03B40/04—Preventing adhesion between glass and glass or between glass and the means used to shape it, hold it or support it using gas
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Description
本発明は高屈折率低分散特性を有する光学ガラス、前記光学ガラスからなるプレス成形用ガラスゴブおよび光学素子とその製造方法、ならびに光学素子ブランクの製造方法に関する。 The present invention relates to an optical glass having a high refractive index and a low dispersion characteristic, a glass gob for press molding made of the optical glass, an optical element, a manufacturing method thereof, and a manufacturing method of an optical element blank.
高屈折率低分散ガラスからなるレンズは、高屈折率高分散ガラスからなるレンズと組み合わせることにより、色収差を補正しつつ、光学系のコンパクト化を可能にする。そのため、撮像光学系やプロジェクタなどの投射光学系を構成する光学素子として非常に重要な位置を占めている。 A lens made of high refractive index and low dispersion glass can be combined with a lens made of high refractive index and high dispersion glass to make the optical system compact while correcting chromatic aberration. Therefore, it occupies a very important position as an optical element constituting a projection optical system such as an imaging optical system or a projector.
特許文献１にはこのような高屈折率低分散ガラスが開示されている。特許文献１が開示するガラスは、屈折率ｎｄが１．７５〜２．００でＴａ２Ｏ５の含有量を０〜２５質量％の範囲としているが、屈折率ｎｄが１．８５以上のガラスは全て多量のＴａ２Ｏ５を含んでいる。これは、屈折率ｎｄ１．７５以上といった高屈折率領域においては、ガラス安定性を確保する上で多量のＴａ２Ｏ５導入が欠かせないからである。このように高屈折率低分散ガラスにおいて、Ｔａ２Ｏ５は主要な成分となっている。 Patent Document 1 discloses such a high refractive index and low dispersion glass. The glass disclosed in Patent Document 1 has a refractive index nd of 1.75 to 2.00 and a Ta 2 O 5 content of 0 to 25% by mass, but has a refractive index nd of 1.85 or more. All contain a large amount of Ta 2 O 5 . This is because, in a high refractive index region such as a refractive index nd of 1.75 or more, it is indispensable to introduce a large amount of Ta 2 O 5 in order to ensure glass stability. Thus, in the high refractive index and low dispersion glass, Ta 2 O 5 is a main component.
ところで、タンタル（Ｔａ）は希少価値が高い元素であり、元々非常に高価な物質である。その上、最近、ワールドワイドにレアメタルの価格が高騰しており、タンタルの供給量も不足している。ガラス製造分野においてもタンタル原料が不足しており、こうした状況が続くと光学機器業界にとって必要不可欠な高屈折率低分散ガラスを安定供給できなくなることが危惧される。
本発明はこのような事情のもとで、安定供給が可能であって、優れたガラス安定性を有する高屈折率低分散光学ガラス、このガラスからなるプレス成形用ガラスゴブおよび光学素子、ならびに光学素子ブランクおよび光学素子のそれぞれの製造方法を提供することを目的とするものである。
Under such circumstances, the present invention is capable of stable supply and has a high refractive index and low dispersion optical glass having excellent glass stability, a glass gob and an optical element for press molding made of this glass, and an optical element An object of the present invention is to provide a blank and an optical element manufacturing method.
本発明者らは、前記目的を達成するために鋭意研究を重ねた結果、特定のガラス組成と屈折率とアッベ数を有する光学ガラスにより、その目的を達成し得ることを見出し、この知見に基づいて本発明を完成するに至った。 As a result of intensive studies to achieve the above object, the present inventors have found that the object can be achieved by an optical glass having a specific glass composition, refractive index, and Abbe number, and based on this finding. The present invention has been completed.
すなわち、上記目的は、下記手段により達成された。
［１］モル％表示で、
ＳｉＯ 2 ０．１〜４０％、
Ｂ 2 Ｏ 3 １０〜５０％、
Ｌｉ 2 Ｏ、Ｎａ 2 ＯおよびＫ 2 Ｏを合計で０〜１０％、
ＭｇＯ、ＣａＯ、ＳｒＯおよびＢａＯを合計で０〜１０％、
ＺｎＯ ０．５〜２２％、
Ｌａ 2 Ｏ 3 ５〜５０％、
Ｇｄ 2 Ｏ 3 ０．１〜２５％、
Ｙ 2 Ｏ 3 ０．１〜２０％、
Ｙｂ 2 Ｏ 3 ０〜２０％、
ＺｒＯ 2 ０〜２５％、
ＴｉＯ 2 ０〜２５％、
Ｎｂ 2 Ｏ 5 ０〜２０％、
Ｔａ 2 Ｏ 5 ０〜７％、
ＷＯ 3 ０．１％を超え２０％以下、
ＧｅＯ 2 ０〜３％未満、
Ｂｉ 2 Ｏ 3 ０〜１０％、
Ａｌ 2 Ｏ 3 ０〜１０％、
を含み、Ｂ 2 Ｏ 3 の含有量に対するＳｉＯ 2 の含有量の質量比ＳｉＯ 2 ／Ｂ 2 Ｏ 3 が１以下であり、
屈折率ｎｄが１．８６〜１．９５、アッベ数νｄが（２．３６−ｎｄ）／０．０１４以上、３８未満、かつガラス転移温度が６４０℃以上であることを特徴とする光学ガラス。
［２］屈折率ｎｄが１．８９〜１．９５、かつアッベ数νｄが（２．３６−ｎｄ）／０．０１４以上、３８未満である［１］に記載の光学ガラス。
［３］ＺｎＯ含有量は０．５〜１８モル％である［１］または［２］に記載の光学ガラス。
［４］Ｇｅフリーガラスである［１］〜［３］のいずれかに記載の光学ガラス。
［５］ＳｉＯ 2 含有量は３〜３５モル％の範囲であり、Ｂ 2 Ｏ 3 含有量は１２〜４５モル％の範囲である［１］〜［４］のいずれかに記載の光学ガラス。
［６］Ｂ 2 Ｏ 3 含有量に対するＳｉＯ 2 含有量の質量比ＳｉＯ 2 ／Ｂ 2 Ｏ 3 は０．９５以下である［１］〜［５］のいずれかに記載の光学ガラス。
［７］Ｌｉ 2 Ｏ、Ｎａ 2 ＯおよびＫ 2 Ｏの合計含有量は０〜８モル％の範囲である［１］〜［６］のいずれかに記載の光学ガラス。
［８］ＭｇＯ、ＣａＯ、ＳｒＯおよびＢａＯの合計含有量は０〜８モル％の範囲である［１］〜［７］のいずれかに記載の光学ガラス。
［９］モル％表示で、
Ｌａ 2 Ｏ 3 ５〜４５％、
Ｇｄ 2 Ｏ 3 ０．１〜２０％、
Ｙ 2 Ｏ 3 ０．１〜１８％、および
Ｙｂ 2 Ｏ 3 ０〜１８％
を含む［１］〜［８］のいずれかに記載の光学ガラス。
［１０］ＺｒＯ 2 含有量は０〜２２モル％の範囲である［１］〜［９］のいずれかに記載の光学ガラス。
［１１］ＴｉＯ 2 含有量は０〜２２モル％の範囲である［１］〜［１０］のいずれかに記載の光学ガラス。
［１２］Ｎｂ 2 Ｏ 5 含有量は０〜１８モル％の範囲である［１］〜［１１］のいずれかに記載の光学ガラス。
［１３］Ｔａ 2 Ｏ 5 含有量は０〜５モル％の範囲である［１］〜［１２］のいずれかに記載の光学ガラス。
［１４］ＷＯ 3 含有量は０．１モル％超１８モル％以下の範囲である［１］〜［１３］のいずれかに記載の光学ガラス。
［１５］Ｂｉ 2 Ｏ 3 含有量は０〜５モル％の範囲である［１］〜［１４］のいずれかに記載の光学ガラス。
［１６］Ａｌ 2 Ｏ 3 含有量は０〜５モル％の範囲である［１］〜［１５］のいずれかに記載の光学ガラス。
［１７］Ｓｂ 2 Ｏ 3 含有量は外割りで０〜１質量％の範囲である［１］〜［１６］のいずれかに記載の光学ガラス。
［１８］ＳｎＯ 2 含有量は外割りで０〜１質量％の範囲である［１］〜［１７］のいずれかに記載の光学ガラス。
［１９］ガラス転移温度は６６０℃以上である［１］〜［１８］のいずれかに記載の光学ガラス。
［２０］ガラス転移温度は７２０℃以下である［１］〜［１９］のいずれかに記載の光学ガラス。
［２１］比重は４．９３〜５．０７の範囲である［１］〜［２０］のいずれかに記載の光学ガラス。
［２２］［１］〜［２１］のいずれかに記載の光学ガラスからなるプレス成形用ガラスゴブ。
［２３］［１］〜［２１］のいずれかに記載の光学ガラスからなる光学素子。
［２４］研削、研磨により光学素子に仕上げられる光学素子ブランクの製造方法において、
［２２］に記載のプレス成形用ガラスゴブを加熱、軟化してプレス成形することを特徴とする光学素子ブランクの製造方法。
［２５］研削、研磨により光学素子に仕上げられる光学素子ブランクの製造方法において、
ガラス原料を熔融し、得られた熔融ガラスをプレス成形し、［１］〜［２１］のいずれかに記載の光学ガラスからなる光学素子ブランクを作製することを特徴とする光学素子ブランクの製造方法。
［２６］［２４］または［２５］に記載の製造方法により光学素子ブランクを作製すること、および作製した光学素子ブランクを研削、研磨することを特徴とする光学素子の製造方法。
That is, the above object has been achieved by the following means.
[1] In mol% display,
SiO 2 0.1-40%,
B 2 O 3 10-50%,
Li 2 O, Na 2 O and K 2 O in total 0 to 10%,
MgO, CaO, SrO and BaO in total 0 to 10%,
ZnO 0.5-22%,
La 2 O 3 5-50%,
Gd 2 O 3 0.1-25%,
Y 2 O 3 0.1-20%,
Yb 2 O 3 0-20%,
ZrO 2 0-25%,
TiO 2 0-25%,
Nb 2 O 5 0-20%,
Ta 2 O 5 0-7%,
WO 3 exceeding 0.1% and 20% or less,
GeO 2 0 to less than 3%,
Bi 2 O 3 0-10%,
Al 2 O 3 0-10%,
Hints, B 2 O 3 mass ratio of the content of SiO 2 SiO 2 / B 2 O 3 to the content of 1 or less,
An optical glass having a refractive index nd of 1.86 to 1.95, an Abbe number νd of (2.36−nd) /0.014 or more and less than 38, and a glass transition temperature of 640 ° C. or more.
[2] The optical glass according to [1], wherein the refractive index nd is 1.89 to 1.95, and the Abbe number νd is (2.36−nd) /0.014 or more and less than 38.
[3] The optical glass according to [1] or [2], wherein the ZnO content is 0.5 to 18 mol%.
[4] The optical glass according to any one of [1] to [3], which is a Ge-free glass.
[5] The optical glass according to any one of [1] to [4], wherein the SiO 2 content is in the range of 3 to 35 mol%, and the B 2 O 3 content is in the range of 12 to 45 mol%.
[6] The optical glass according to any one of [1] to [5], wherein a mass ratio SiO 2 / B 2 O 3 of SiO 2 content to B 2 O 3 content is 0.95 or less.
[7] The optical glass according to any one of [1] to [6], wherein the total content of Li 2 O, Na 2 O and K 2 O is in the range of 0 to 8 mol%.
[8] The optical glass according to any one of [1] to [7], wherein the total content of MgO, CaO, SrO and BaO is in the range of 0 to 8 mol%.
[9] In mol% display,
La 2 O 3 5-45%,
Gd 2 O 3 0.1-20%,
Y 2 O 3 0.1-18%, and
Yb 2 O 3 0-18%
The optical glass according to any one of [1] to [8].
[10] The optical glass according to any one of [1] to [9], wherein the ZrO 2 content is in the range of 0 to 22 mol%.
[11] The optical glass according to any one of [1] to [10], wherein the content of TiO 2 is in the range of 0 to 22 mol%.
[12] The optical glass according to any one of [1] to [11], wherein the Nb 2 O 5 content is in the range of 0 to 18 mol%.
[13] The optical glass according to any one of [1] to [12], wherein the content of Ta 2 O 5 is in the range of 0 to 5 mol%.
[14] The optical glass according to any one of [1] to [13], wherein the content of WO 3 is in the range of more than 0.1 mol% and 18 mol% or less.
[15] The optical glass according to any one of [1] to [14], wherein the Bi 2 O 3 content is in the range of 0 to 5 mol%.
[16] The optical glass according to any one of [1] to [15], wherein the Al 2 O 3 content is in the range of 0 to 5 mol%.
[17] The optical glass according to any one of [1] to [16], in which the Sb 2 O 3 content is in an externally range of 0 to 1% by mass.
[18] The optical glass according to any one of [1] to [17], in which the SnO 2 content is in the range of 0 to 1% by mass.
[19] The optical glass according to any one of [1] to [18], which has a glass transition temperature of 660 ° C. or higher.
[20] The optical glass according to any one of [1] to [19], which has a glass transition temperature of 720 ° C. or lower.
[21] The optical glass according to any one of [1] to [20], wherein the specific gravity is in the range of 4.93 to 5.07.
[22] A glass gob for press molding comprising the optical glass according to any one of [1] to [21].
[23] An optical element comprising the optical glass according to any one of [1] to [21].
[24] In a method for manufacturing an optical element blank that is finished into an optical element by grinding and polishing,
A method for producing an optical element blank, comprising heating and softening the press-molding glass gob according to [22] to perform press molding.
[25] In a method for producing an optical element blank that is finished into an optical element by grinding and polishing,
A method for producing an optical element blank, comprising melting a glass raw material, press-molding the obtained molten glass, and producing an optical element blank made of the optical glass according to any one of [1] to [21]. .
[26] A method for producing an optical element, comprising producing an optical element blank by the production method according to [24] or [25], and grinding and polishing the produced optical element blank.
本発明によれば、安定供給が可能であって、優れたガラス安定性を有する高屈折率低分散光学ガラス、この光学ガラスからなるプレス成形用ガラスゴブおよび光学素子、並びに、光学素子ブランクおよび光学素子のそれぞれの製造方法を提供することができる。 According to the present invention, a high-refractive index low-dispersion optical glass that can be stably supplied and has excellent glass stability, a glass gob and an optical element for press molding made of this optical glass, and an optical element blank and an optical element The respective manufacturing methods can be provided.
［光学ガラス］
まず、本発明の光学ガラスについて説明する。
[Optical glass]
First, the optical glass of the present invention will be described.
本発明の光学ガラスにおいては、ガラス成分の中でも特に高価なＴａ２Ｏ５の導入量を低減、制限する。こうした制限下、耐失透性を維持しつつ高屈折率低分散特性を付与するには、単にＴａ２Ｏ５の量を削減するだけでは、ガラス化しなかったり、生産過程でガラスが失透して使い物にならなくなってしまう。こうした問題を回避しつつ、Ｔａ２Ｏ５の導入量を削減するには、高屈折率付与成分の配分が重要である。 In the optical glass of the present invention, the amount of Ta 2 O 5 that is particularly expensive among the glass components is reduced and limited. Under these restrictions, in order to provide high refractive index and low dispersion characteristics while maintaining devitrification resistance, simply reducing the amount of Ta 2 O 5 does not cause vitrification or the glass is devitrified in the production process. Will not be useful. In order to reduce the amount of Ta 2 O 5 introduced while avoiding such problems, it is important to distribute the high refractive index imparting component.
本発明では、ガラスの網目形成酸化物としてＢ２Ｏ３、ＳｉＯ２を導入するとともに、高屈折率付与成分であるＬａ２Ｏ３、Ｇｄ２Ｏ３、Ｙ２Ｏ３、ＷＯ３、ＺｎＯを必須成分として共存させる。本発明においてＺｎＯは熔解性の向上、ガラス転移温度の低下だけでなく、高屈折率低分散化と耐失透性向上に寄与する重要な成分である。 In the present invention, B 2 O 3 and SiO 2 are introduced as glass network-forming oxides, and La 2 O 3 , Gd 2 O 3 , Y 2 O 3 , WO 3 and ZnO which are high refractive index imparting components are added. Coexist as an essential ingredient. In the present invention, ZnO is an important component that contributes not only to improving meltability and lowering the glass transition temperature, but also to lowering the high refractive index and improving devitrification resistance.
その上で、Ｂ２Ｏ３量とＳｉＯ２量のバランスを調整して耐失透性、熔解性、熔融ガラスの成形性を改善し、他成分とのバランスを図ることにより、上記発明の目的を達成したものである。 Then, by adjusting the balance between the B 2 O 3 amount and the SiO 2 amount to improve the devitrification resistance, the melting property, and the moldability of the molten glass, the object of the invention is achieved by balancing with other components. Is achieved.
本発明の光学ガラスは、モル％表示で、
ＳｉＯ２ ０．１〜４０％、
Ｂ２Ｏ３ １０〜５０％、
Ｌｉ２Ｏ、Ｎａ２ＯおよびＫ２Ｏを合計で０〜１０％、
ＭｇＯ、ＣａＯ、ＳｒＯおよびＢａＯを合計で０〜１０％、
ＺｎＯ ０．５〜２２％、
Ｌａ２Ｏ３ ５〜５０％、
Ｇｄ２Ｏ３ ０．１〜２５％、
Ｙ２Ｏ３ ０．１〜２０％、
Ｙｂ２Ｏ３ ０〜２０％、
ＺｒＯ２ ０〜２５％、
ＴｉＯ２ ０〜２５％、
Ｎｂ２Ｏ５ ０〜２０％、
Ｔａ２Ｏ５ ０〜１０％、
ＷＯ３ ０．１％を超え２０％以下、
ＧｅＯ２ ０〜３％未満、
Ｂｉ２Ｏ３ ０〜１０％、
Ａｌ２Ｏ３ ０〜１０％、
を含み、Ｂ２Ｏ３の含有量に対するＳｉＯ２の含有量の質量比ＳｉＯ２／Ｂ２Ｏ３が１以下であり、
屈折率ｎｄが１．８６〜１．９５、アッベ数νｄが（２．３６−ｎｄ）／０．０１４以上、３８未満であることを特徴とする。
（組成範囲の限定理由）
上記組成範囲の限定理由について説明するが、特記しない限り、各成分の含有量、合計含有量はモル％にて表示する。
The optical glass of the present invention is expressed in mol%,
SiO 2 0.1~40%,
B 2 O 3 10-50%,
Li 2 O, Na 2 O and K 2 O in total 0 to 10%,
MgO, CaO, SrO and BaO in total 0 to 10%,
ZnO 0.5-22%,
La 2 O 3 5-50%,
Gd 2 O 3 0.1-25%,
Y 2 O 3 0.1-20%,
Yb 2 O 3 0-20%,
ZrO 2 0-25%,
TiO 2 0-25%,
Nb 2 O 5 0-20%,
Ta 2 O 5 0-10%,
WO 3 exceeding 0.1% and 20% or less,
GeO 2 0 to less than 3%,
Bi 2 O 3 0-10%,
Al 2 O 3 0-10%,
Hints, B 2 O 3 mass ratio of the content of SiO 2 SiO 2 / B 2 O 3 to the content of 1 or less,
The refractive index nd is 1.86 to 1.95, and the Abbe number νd is (2.36−nd) /0.014 or more and less than 38.
(Reason for limitation of composition range)
The reason for limiting the composition range will be described. Unless otherwise specified, the content and total content of each component are expressed in mol%.
ＳｉＯ２は、網目形成酸化物であり、ガラス安定性の維持および熔融ガラスの成形に適した粘性の維持に必要な必須成分であり、その量が０．１％未満であるとガラスの安定性が低下し、熔融ガラス成形時のガラスの粘性も低下して成形性が悪化してしまう。また、化学的耐久性も低下してしまう。一方、その量が４０％を超えると所望の屈折率を実現することが困難になるとともに、液相温度やガラス転移温度が上昇してしまう。また、所望のアッベ数を実現することが困難になる、ガラスの熔融性が悪化する、耐失透性が悪化するなどの問題が生じてしまう。したがって、ＳｉＯ２の含有量は０．１〜４０％とする。ＳｉＯ２の含有量の好ましい範囲は３〜３５％、より好ましい範囲は５〜３０％、さらに好ましい範囲は５〜２５％、一層好ましい範囲は７〜２２％、より一層好ましい範囲は１０〜２０％である。 SiO 2 is a network-forming oxide, and is an essential component necessary for maintaining glass stability and viscosity suitable for forming molten glass. If the amount is less than 0.1%, stability of the glass is required. Decreases, the viscosity of the glass at the time of molding molten glass also decreases, and the moldability deteriorates. Moreover, chemical durability will also fall. On the other hand, when the amount exceeds 40%, it becomes difficult to achieve a desired refractive index, and the liquidus temperature and the glass transition temperature increase. In addition, problems such as difficulty in realizing a desired Abbe number, deterioration in glass meltability, and deterioration in devitrification resistance occur. Therefore, the content of SiO 2 is set to 0.1 to 40%. The preferable range of the content of SiO 2 is 3 to 35%, the more preferable range is 5 to 30%, the further preferable range is 5 to 25%, the more preferable range is 7 to 22%, and the still more preferable range is 10 to 20%. It is.
Ｂ２Ｏ３は、網目形成酸化物であり、ガラスの熔融性維持、液相温度の低下に有効な必須成分である。また、低分散特性を付与する上からも有効な成分である。その量が１０％未満になるとガラス安定性が低下し、５０％を超えると所望の屈折率を満たすことが困難になるとともに、化学的耐久性が悪化する。したがって、Ｂ２Ｏ３の含有量は１０〜５０％とする。Ｂ２Ｏ３の含有量の好ましい範囲は１２〜４５％、より好ましい範囲は１５〜４３％、さらに好ましい範囲は１７〜４０％、一層好ましい範囲は１７〜３８％、より一層好ましい範囲は１８〜３５％である。 B 2 O 3 is a network-forming oxide and is an essential component effective for maintaining the meltability of the glass and lowering the liquidus temperature. It is also an effective component from the viewpoint of imparting low dispersion characteristics. When the amount is less than 10%, the glass stability is lowered, and when it exceeds 50%, it is difficult to satisfy a desired refractive index and the chemical durability is deteriorated. Therefore, the content of B 2 O 3 is 10 to 50%. A preferable range of the content of B 2 O 3 is 12 to 45%, a more preferable range is 15 to 43%, a further preferable range is 17 to 40%, a more preferable range is 17 to 38%, and a still more preferable range is 18 to 35%.
なお、液相温度の低下、耐失透性の改善および熔融性の改善のため、また、成形に適した粘性を維持する上から、Ｂ２Ｏ３の含有量に対するＳｉＯ２の含有量の質量比ＳｉＯ２／Ｂ２Ｏ３は１以下とする。前記質量比ＳｉＯ２／Ｂ２Ｏ３は、質量％表示によるＳｉＯ２の含有量をＢ２Ｏ３の含有量で割った値である。前記比が１を超えると液相温度が上昇するとともに耐失透性が悪化し、熔融性も悪化し、所望のアッべ数を実現することも困難になる。 In addition, the mass of the content of SiO 2 with respect to the content of B 2 O 3 from the viewpoint of lowering the liquidus temperature, improving devitrification resistance and improving meltability, and maintaining viscosity suitable for molding The ratio SiO 2 / B 2 O 3 is 1 or less. The mass ratio SiO 2 / B 2 O 3 is a value obtained by dividing the content of SiO 2 by mass% display by the content of B 2 O 3 . When the ratio exceeds 1, the liquidus temperature rises and the devitrification resistance deteriorates, the meltability also deteriorates, and it becomes difficult to realize a desired Abbe number.
質量比ＳｉＯ２／Ｂ２Ｏ３の好ましい範囲は０．９５以下、より好ましい範囲は０．９０以下である。 A preferable range of the mass ratio SiO 2 / B 2 O 3 is 0.95 or less, and a more preferable range is 0.90 or less.
Ｌｉ２Ｏ、Ｎａ２ＯおよびＫ２Ｏは、熔融性を改善し、ガラス転移温度を低下させる働きをする任意成分である。Ｌｉ２Ｏ、Ｎａ２ＯおよびＫ２Ｏの合計含有量が１０％を超えると所望の屈折率を実現するのが困難になり、化学的耐久性も低下する。したがって、Ｌｉ２Ｏ、Ｎａ２ＯおよびＫ２Ｏの合計含有量は０〜１０％とする。Ｌｉ２Ｏ、Ｎａ２ＯおよびＫ２Ｏの合計含有量の好ましい範囲は０〜８％、より好ましい範囲は０〜６％、さらに好ましい範囲は０〜４％、一層好ましい範囲は０〜２％であり、上記アルカリ金属酸化物を含まないことがより一層好ましい。 Li 2 O, Na 2 O and K 2 O are optional components that work to improve meltability and lower the glass transition temperature. If the total content of Li 2 O, Na 2 O and K 2 O exceeds 10%, it becomes difficult to realize a desired refractive index, and chemical durability is also lowered. Therefore, the total content of Li 2 O, Na 2 O and K 2 O is 0 to 10%. A preferable range of the total content of Li 2 O, Na 2 O and K 2 O is 0 to 8%, a more preferable range is 0 to 6%, a further preferable range is 0 to 4%, and a more preferable range is 0 to 2%. It is even more preferable not to include the alkali metal oxide.
ＭｇＯ、ＣａＯ、ＳｒＯおよびＢａＯは、ガラスの熔融性や可視域における光線透過率を改善する働きをする。また、炭酸塩や硝酸塩の形でガラスに導入することにより、脱泡効果も得られる。しかし、その量が１０％を超えると液相温度が上昇し、耐失透性が悪化するほか、屈折率が低下し、化学的耐久性も悪化してしまう。したがって、ＭｇＯ、ＣａＯ、ＳｒＯおよびＢａＯの合計含有量を０〜１０％とする。ＭｇＯ、ＣａＯ、ＳｒＯおよびＢａＯの合計含有量の好ましい範囲は０〜８％、より好ましい範囲は０〜６％、さらに好ましい範囲は０〜４％、一層好ましい範囲は０〜２％である。アルカリ土類金属酸化物を含まないことがより一層好ましい。 MgO, CaO, SrO and BaO function to improve the meltability of the glass and the light transmittance in the visible range. Moreover, the defoaming effect is also acquired by introduce | transducing into glass in the form of carbonate or nitrate. However, if the amount exceeds 10%, the liquidus temperature rises, the devitrification resistance deteriorates, the refractive index decreases, and the chemical durability also deteriorates. Therefore, the total content of MgO, CaO, SrO and BaO is set to 0 to 10%. A preferable range of the total content of MgO, CaO, SrO and BaO is 0 to 8%, a more preferable range is 0 to 6%, a further preferable range is 0 to 4%, and a more preferable range is 0 to 2%. It is even more preferable not to include alkaline earth metal oxides.
ＺｎＯは、高屈折率低分散特性を実現する上で有用な必須成分であり、ガラスの熔融性、耐失透性を改善し、液相温度やガラス転移温度を低下させる働きをする。その量が０．５％未満であると屈折率が低下したり、液相温度が上昇し、耐失透性が悪化する。一方、その量が２２％を越えると所望の屈折率を実現することが困難になる。したがって、ＺｎＯの含有量は０．５〜２２％とする。ＺｎＯの含有量のより好ましい範囲は０．５〜２０％、さらに好ましい範囲は１〜１８％、一層好ましい範囲は２〜１７％、より一層好ましい範囲は３〜１７％、なお一層好ましい範囲は４〜１７％である。 ZnO is an essential component useful for realizing high refractive index and low dispersion characteristics, and functions to improve the meltability and devitrification resistance of glass and lower the liquidus temperature and glass transition temperature. If the amount is less than 0.5%, the refractive index decreases, the liquidus temperature rises, and devitrification resistance deteriorates. On the other hand, if the amount exceeds 22%, it becomes difficult to achieve a desired refractive index. Therefore, the ZnO content is set to 0.5 to 22%. A more preferable range of the content of ZnO is 0.5 to 20%, a further preferable range is 1 to 18%, a more preferable range is 2 to 17%, a still more preferable range is 3 to 17%, and an even more preferable range is 4 ~ 17%.
Ｌａ２Ｏ３は、高屈折率低分散特性を実現する上で必須であり、化学的耐久性を改善する働きもする。その量が５％未満であると所望の屈折率が得にくくなり、５０％を超えると液相温度が上昇し、耐失透性が悪化する。したがって、Ｌａ２Ｏ３の含有量は５〜５０％とする。Ｌａ２Ｏ３の含有量の好ましい範囲は５〜４５％、より好ましい範囲は５〜４０％、さらに好ましい範囲は５〜３５％、一層好ましい範囲は７〜３０％、より一層好ましい範囲は１０〜２５％である。 La 2 O 3 is essential for realizing a high refractive index and low dispersion characteristic, and also serves to improve chemical durability. If the amount is less than 5%, it becomes difficult to obtain a desired refractive index, and if it exceeds 50%, the liquidus temperature rises and devitrification resistance deteriorates. Therefore, the content of La 2 O 3 is set to 5 to 50%. The preferable range of the content of La 2 O 3 is 5 to 45%, the more preferable range is 5 to 40%, the further preferable range is 5 to 35%, the more preferable range is 7 to 30%, and the still more preferable range is 10 to 10. 25%.
Ｇｄ２Ｏ３は、Ｌａ２Ｏ３と共存させることにより液相温度を低下させ、耐失透性を大幅に改善する働きをする。その量が０．１％未満であると屈折率が低下し、液相温度が上昇、耐失透性や化学的耐久性が悪化する。一方、その量が２５％を超えると液相温度が上昇し、耐失透性が悪化する。したがって、Ｇｄ２Ｏ３の含有量は０．１〜２５％とする。Ｇｄ２Ｏ３の含有量の好ましい範囲は０．１〜２０％、より好ましい範囲は０．１〜１８％、さらに好ましい範囲は０．１〜１５％、一層好ましい範囲は０．１〜１２％、より一層好ましい範囲は０．１〜１０％、なお一層好ましい範囲は１〜１０％である。 Gd 2 O 3 serves to lower the liquidus temperature by coexisting with La 2 O 3 and greatly improve devitrification resistance. If the amount is less than 0.1%, the refractive index decreases, the liquidus temperature rises, and devitrification resistance and chemical durability deteriorate. On the other hand, if the amount exceeds 25%, the liquidus temperature rises and the devitrification resistance deteriorates. Therefore, the content of Gd 2 O 3 is set to 0.1 to 25%. A preferable range of the content of Gd 2 O 3 is 0.1 to 20%, a more preferable range is 0.1 to 18%, a further preferable range is 0.1 to 15%, and a more preferable range is 0.1 to 12%. A more preferable range is 0.1 to 10%, and an even more preferable range is 1 to 10%.
Ｙ２Ｏ３もＬａ２Ｏ３と共存させることにより液相温度を低下させ、耐失透性を大幅に改善する働きをする。その量が０．１％未満であると屈折率が低下し、液相温度が上昇、耐失透性や化学的耐久性が悪化する。一方、その量が２０％を超えると液相温度が上昇し、耐失透性が悪化する。したがって、Ｙ２Ｏ３の含有量は０．１〜２０％とする。Ｙ２Ｏ３の含有量の好ましい範囲は０．１〜１８％、より好ましい範囲は０．１〜１５％、さらに好ましい範囲は０．１〜１３％、一層好ましい範囲は０．１〜１０％、より一層好ましい範囲は０．１〜７％．なお一層好ましい範囲は５〜７％である。 Y 2 O 3 coexists with La 2 O 3 to lower the liquidus temperature and greatly improve the devitrification resistance. If the amount is less than 0.1%, the refractive index decreases, the liquidus temperature rises, and devitrification resistance and chemical durability deteriorate. On the other hand, when the amount exceeds 20%, the liquidus temperature rises and the devitrification resistance deteriorates. Therefore, the content of Y 2 O 3 is set to 0.1 to 20%. A preferred range for the content of Y 2 O 3 is 0.1 to 18%, a more preferred range is 0.1 to 15%, a further preferred range is 0.1 to 13%, and a more preferred range is 0.1 to 10%. The more preferable range is 0.1 to 7%. A still more preferable range is 5 to 7%.
Ｙｂ２Ｏ３もＬａ２Ｏ３と共存させることにより液相温度を低下させ、耐失透性を大幅に改善する働きをする。その量が２０％を超えると液相温度が上昇し、耐失透性が悪化する。したがって、Ｙｂ２Ｏ３の含有量は０〜２０％とする。Ｙｂ２Ｏ３の含有量の好ましい範囲は０〜１８％、より好ましい範囲は０〜１６％、さらに好ましい範囲は０〜１４％、一層好ましい範囲は０〜１２％、より一層好ましい範囲は０〜１０％、なお一層好ましい範囲は０〜５％である。 Yb 2 O 3 coexists with La 2 O 3 to lower the liquidus temperature and greatly improve the devitrification resistance. If the amount exceeds 20%, the liquidus temperature rises and the devitrification resistance deteriorates. Therefore, the content of Yb 2 O 3 is set to 0 to 20%. A preferred range for the content of Yb 2 O 3 is 0 to 18%, a more preferred range is 0 to 16%, a further preferred range is 0 to 14%, a more preferred range is 0 to 12%, and a still more preferred range is 0 to 0%. 10%, an even more preferred range is 0-5%.
ＺｒＯ２は、屈折率を高め、化学的耐久性を改善する働きをする。少量の導入でも優れた効果が得られる。しかし、その量が２５％を超えると、ガラス転移温度や液相温度が上昇し、耐失透性が低下する。したがって、ＺｒＯ２の含有量は０〜２５％とする。ＺｒＯ２の含有量の好ましい範囲は０〜２２％、より好ましい範囲は２〜２２％、さらに好ましい範囲は２〜２０％、一層好ましい範囲は２〜１８％、より一層好ましい範囲は２〜１５％、なお一層好ましい範囲は２〜１３％である。 ZrO 2 functions to increase the refractive index and improve chemical durability. Excellent effects can be obtained even with a small amount of introduction. However, if the amount exceeds 25%, the glass transition temperature and the liquidus temperature increase, and the devitrification resistance decreases. Therefore, the content of ZrO 2 is set to 0 to 25%. The preferable range of the content of ZrO 2 is 0 to 22%, the more preferable range is 2 to 22%, the further preferable range is 2 to 20%, the more preferable range is 2 to 18%, and the still more preferable range is 2 to 15%. An even more preferred range is 2 to 13%.
ＴｉＯ２は、屈折率を高め、化学的耐久性および耐失透性を改善する働きをする。しかし、その量が２５％を超えると所望のアッベ数を得ることが難しくなるとともに、ガラス転移温度や液相温度が上昇し、耐失透性が悪化する。したがって、ＴｉＯ２の含有量は０〜２５％とする。ＴｉＯ２の含有量の好ましい範囲は０〜２２％、より好ましい範囲は３〜２０％、さらに好ましい範囲は３〜１８％、一層好ましい範囲は３〜１７％、より一層好ましい範囲は３〜１６％である。 TiO 2 serves to increase the refractive index and improve chemical durability and resistance to devitrification. However, when the amount exceeds 25%, it becomes difficult to obtain a desired Abbe number, and the glass transition temperature and the liquidus temperature are increased, so that the devitrification resistance is deteriorated. Therefore, the content of TiO 2 is set to 0 to 25%. The preferable range of the content of TiO 2 is 0 to 22%, the more preferable range is 3 to 20%, the further preferable range is 3 to 18%, the more preferable range is 3 to 17%, and the still more preferable range is 3 to 16%. It is.
Ｎｂ２Ｏ５は、屈折率を高めるとともに、液相温度を低下させ、耐失透性を改善する働きをする。その量が２０％を超えると液相温度が上昇し、耐失透性が悪化し、所望のアッベ数を実現することが困難になるほか、ガラスの着色も強まる。したがって、Ｎｂ２Ｏ５の含有量を０〜２０％とする。Ｎｂ２Ｏ５の含有量の好ましい範囲は０〜１８％、より好ましい範囲は０〜１５％、さらに好ましい範囲は０〜１２％、一層好ましい範囲は０〜１０％、より一層好ましい範囲は0〜8％である。 Nb 2 O 5 functions to increase the refractive index, lower the liquidus temperature, and improve devitrification resistance. If the amount exceeds 20%, the liquidus temperature rises, the devitrification resistance deteriorates, it becomes difficult to achieve the desired Abbe number, and the coloring of the glass also increases. Therefore, the content of Nb 2 O 5 is set to 0 to 20%. The preferable range of the content of Nb 2 O 5 is 0 to 18%, the more preferable range is 0 to 15%, the further preferable range is 0 to 12%, the more preferable range is 0 to 10%, and the still more preferable range is 0 to 0%. 8%.
Ｔａ２Ｏ５は、高屈折率低分散性を実現し、ガラス安定性も高める働きをするが、高価な成分であるため、本発明の目的である高屈折率低分散ガラスの安定供給を達成するため、その含有量を１０％以下に抑える。また、その含有量が１０％を超えると液相温度が上昇し、耐失透性が悪化する。したがって、Ｔａ２Ｏ５の含有量は０〜１０％とする。Ｔａ２Ｏ５の含有量の好ましい範囲は０〜７％、より好ましい範囲は０〜５％、さらに好ましい範囲は０〜４％、一層好ましい範囲は０〜３％、より一層好ましい範囲は０〜２％、なお一層好ましい範囲は０〜１％である。Ｔａ２Ｏ５を含まないことが特に好ましい。 Ta 2 O 5 achieves a high refractive index and low dispersion and works to increase the stability of the glass. However, since Ta 2 O 5 is an expensive component, it achieves the stable supply of the high refractive index and low dispersion glass that is the object of the present invention. Therefore, the content is suppressed to 10% or less. Moreover, when the content exceeds 10%, liquidus temperature will rise and devitrification resistance will deteriorate. Therefore, the content of Ta 2 O 5 is set to 0 to 10%. The preferable range of the content of Ta 2 O 5 is 0 to 7%, the more preferable range is 0 to 5%, the further preferable range is 0 to 4%, the more preferable range is 0 to 3%, and the still more preferable range is 0 to 0%. 2%, an even more preferred range is 0 to 1%. It is particularly preferable not to include Ta 2 O 5 .
ＷＯ3は、屈折率を高め、液相温度を低下させ、耐失透性の改善に寄与する必須成分である。その量が０．１％以下であると所望の屈折率を得ることが困難になるとともに、液相温度が上昇し、耐失透性が悪化してしまう。一方、その量が２０％を越えると液相温度が上昇し、耐失透性が悪化してしまう。また、ガラスの着色も強まる。したがって、ＷＯ3の含有量は、０．１％を超え２０％以下とする。ＷＯ3の含有量の好ましい範囲は０．１％超１８％以下、より好ましい範囲は０．１％超１５％以下、さらに好ましい範囲は０．５〜１０％、一層好ましい範囲は０．５〜８％、より一層好ましい範囲は０．５〜７％である。 WO 3 is an essential component that increases the refractive index, lowers the liquidus temperature, and contributes to the improvement of devitrification resistance. Together with the amount is difficult to obtain a desired refractive index and Ru der 0.1% or less, the liquidus temperature increases, devitrification resistance is deteriorated. On the other hand, if the amount exceeds 20%, the liquidus temperature rises and the devitrification resistance deteriorates. In addition, the coloring of the glass is strengthened. Therefore, the content of WO 3 is more than 0.1% and not more than 20%. WO 3 preferred range of the content is from 0.1 percent 18 percent or less, and more preferably ranges from 0.1 percent to 15% or less, still more preferably in the range of 0.5% to 10%, yet more preferably in the range 0.5 to 8%, and a more preferable range is 0.5 to 7%.
ＧｅＯ２は、網目形成酸化物であり、屈折率を高める働きもするため、ガラス安定性を維持しつつ屈折率を高めることができる成分であるが、非常に高価な成分であり、Ｔａ成分とともに、その量を控えることが望まれる成分である。本発明では、上記のように組成を決めているので、ＧｅＯ２の含有量を３％未満に抑えても、所望の光学特性の実現と優れたガラス安定性の実現を両立することができる。従ってＧｅＯ２の含有量は０〜３％未満とする。ＧｅＯ２の含有量の好ましい範囲は０〜２％、より好ましい範囲は０〜１％、さらに好ましい範囲は０〜０．５％であり、ＧｅＯ２を含まないこと、すなわちＧｅフリーガラスであることが特に好ましい。 GeO 2 is a network-forming oxide, and also functions to increase the refractive index. Therefore, GeO 2 is a component that can increase the refractive index while maintaining glass stability, but it is a very expensive component and together with the Ta component. , An ingredient that it is desirable to refrain from. In the present invention, since the composition is determined as described above, it is possible to achieve both desired optical characteristics and excellent glass stability even if the GeO 2 content is suppressed to less than 3%. Therefore, the content of GeO 2 is 0 to less than 3%. The preferable range of the content of GeO 2 is 0 to 2%, the more preferable range is 0 to 1%, and the further preferable range is 0 to 0.5%, and it does not contain GeO 2 , that is, is a Ge-free glass. Is particularly preferred.
Ｂｉ２Ｏ３は、屈折率を高めるとともにガラス安定性も高める働きをするが、その量が１０％を超えると可視域における光線透過率が低下する。したがって、Ｂｉ２Ｏ３の含有量は０〜１０％とする。Ｂｉ２Ｏ３の含有量の好ましい範囲は０〜５％、より好ましい範囲は０〜２％、さらに好ましい範囲は０〜１％であり、Ｂｉ２Ｏ３を含まないことが特に好ましい。 Bi 2 O 3 functions to increase the refractive index and the glass stability. However, when the amount exceeds 10%, the light transmittance in the visible region decreases. Therefore, the content of Bi 2 O 3 is set to 0 to 10%. A preferable range of the content of Bi 2 O 3 is 0 to 5%, a more preferable range is 0 to 2%, a further preferable range is 0 to 1%, and it is particularly preferable that Bi 2 O 3 is not included.
Ａｌ２Ｏ３は、少量であればガラス安定性および化学的耐久性を改善する働きをするが、その量が１０％を超えると液相温度が上昇し、耐失透性が悪化する。したがって、Ａｌ２Ｏ３の含有量は０〜１０％とする。Ａｌ２Ｏ３の含有量の好ましい範囲は０〜５％、より好ましい範囲は０〜２％、さらに好ましい範囲は０〜１％であり、Ａｌ２Ｏ３を含まないことが特に好ましい。 Al 2 O 3 works to improve glass stability and chemical durability when it is in a small amount, but when its amount exceeds 10%, the liquidus temperature rises and devitrification resistance deteriorates. Therefore, the content of Al 2 O 3 is set to 0 to 10%. A preferable range of the content of Al 2 O 3 is 0 to 5%, a more preferable range is 0 to 2%, a further preferable range is 0 to 1%, and it is particularly preferable that Al 2 O 3 is not included.
Ｓｂ２Ｏ３は、清澄剤として添加可能であり、少量の添加でＦｅなどの不純物混入による光線透過率の低下を抑える働きもするが、外割りで１質量％を超えて添加するとガラスが着色したり、その強力な酸化作用によってプレス成形時、プレス成形型の成形面劣化を助長してしまう。したがって、Ｓｂ２Ｏ３の添加量は、外割りで０〜１質量％が好ましく、より好ましくは０〜０．５質量％とする。 Sb 2 O 3 can be added as a refining agent, and also functions to suppress a decrease in light transmittance due to mixing of impurities such as Fe when added in a small amount, but when added more than 1% by mass, the glass is colored. Or the strong oxidizing action promotes deterioration of the molding surface of the press mold during press molding. Therefore, the addition amount of Sb 2 O 3 is preferably 0 to 1% by mass, more preferably 0 to 0.5% by mass, on an external basis.
ＳｎＯ２も清澄剤として添加可能であるが、外割りで１質量％を超えて添加するとガラスが着色したり、酸化作用によって精密プレス成形時、プレス成形型の成形面劣化を助長してしまう。したがって、ＳｎＯ２の添加量を外割りで０〜１質量％が好ましく、より好ましくは０〜０．５質量％とする。 SnO 2 can also be added as a refining agent, but if added in excess of 1% by mass, the glass is colored, or the surface of the press mold is deteriorated during precision press molding due to oxidation. Therefore, the addition amount of SnO 2 is preferably 0 to 1% by mass, and more preferably 0 to 0.5% by mass.
本発明の光学ガラスは、ガラス安定性を維持しつつ高屈折率低分散の光学特性を実現しており、Ｌｕ、Ｈｆといった成分を含有させることを必要としない。Ｌｕ、Ｈｆも高価な成分なので、Ｌｕ２Ｏ３、ＨｆＯ２の含有量をそれぞれ０〜１％に抑えることが好ましく、それぞれ０〜０．５％に抑えることがより好ましく、Ｌｕ２Ｏ３を導入しないこと、ＨｆＯ２を導入しないことがそれぞれ特に好ましい。 The optical glass of the present invention realizes optical characteristics of high refractive index and low dispersion while maintaining glass stability, and does not need to contain components such as Lu and Hf. Lu, because Hf is also an expensive component, it is preferable to suppress Lu 2 O 3, HfO 2 content of 0 to 1%, respectively, more preferably kept to 0 to 0.5%, respectively, the Lu 2 O 3 It is particularly preferable that no introduction or HfO 2 is introduced.
また、環境影響に配慮し、Ａｓ、Ｐｂ、Ｕ、Ｔｈ、Ｔｅ、Ｃｄも導入しないことが好ましい。 In consideration of environmental impact, it is preferable not to introduce As, Pb, U, Th, Te, or Cd.
さらに、ガラスの優れた光線透過性を活かす上から、Ｃｕ、Ｃｒ、Ｖ、Ｆｅ、Ｎｉ、Ｃｏなどの着色の要因となる物質を導入しないことが好ましい。
（光学ガラスの特性）
本発明の光学ガラスの屈折率ｎｄは、１．８６〜１．９５である。屈折率ｎｄの好ましい下限は１．８７、より好ましい下限は１．８８、さらに好ましい下限は１．８９であり、好ましい上限は１．９４、より好ましい上限は１．９３、さらに好ましい上限は１．９２である。
Furthermore, it is preferable not to introduce a substance that causes coloring such as Cu, Cr, V, Fe, Ni, and Co from the viewpoint of taking advantage of the excellent light transmittance of glass.
(Characteristics of optical glass)
The optical glass of the present invention has a refractive index nd of 1.86 to 1.95. The preferable lower limit of the refractive index nd is 1.87, the more preferable lower limit is 1.88, the still more preferable lower limit is 1.89, the preferable upper limit is 1.94, the more preferable upper limit is 1.93, and the further preferable upper limit is 1. 92.
アッベ数νｄが小さいガラス、すなわち分散が高いガラスのほうが、安定性を維持しつつ、屈折率を高めやすい。したがって、本発明は、アッベ数νｄの下限を屈折率ｎｄとの関係で規定する。本発明の光学ガラスのアッベ数νｄは（２．３６−ｎｄ）／０．０１４以上、３８未満である。アッベ数νｄの好ましい下限は（２．３５６−ｎｄ）／０．０１３７である。 A glass having a smaller Abbe number νd, that is, a glass having higher dispersion, can easily increase the refractive index while maintaining stability. Therefore, the present invention defines the lower limit of the Abbe number νd in relation to the refractive index nd. The Abbe number νd of the optical glass of the present invention is (2.36−nd) /0.014 or more and less than 38. A preferred lower limit of the Abbe's number νd is /0.013 7 (2.356-nd).
本発明の光学ガラスは、研削、研磨により平滑な光学機能面を形成するのに好適なガラスである。研削、研磨などの冷間加工の適性、すなわち冷間加工性は間接的ながらガラス転移温度と関連がある。ガラス転移温度が低いガラスは冷間加工性よりも精密プレス成形に好適であるのに対し、ガラス転移温度が高いガラスは精密プレス成形よりも冷間加工に好適であって、冷間加工性に優れる。したがって、本発明においても冷間加工性を優先する場合は、ガラス転移温度を過剰に低くしないことが好ましく、６３０℃よりも高くすることが好ましく、６４０℃以上にすることがより好ましく、６６０℃以上にすることがさらに好ましい。しかし、ガラス転移温度が高すぎるとガラスを再加熱、軟化して成形する際の加熱温度が高くなり、成形に使用する金型の劣化が著しくなったり、アニール温度も高温になり、アニール炉の劣化、消耗も著しくなる。したがって、ガラス転移温度は７２０℃以下とすることが好ましく、７１０℃以下にすることがより好ましく、７００℃未満にすることがさらに好ましい。
（光学ガラスの製造方法）
次に本発明の光学ガラスの製造方法について説明する。例えば、粉体状の化合物原料あるいはカレット原料を目的のガラス組成に対応して秤量、調合し、白金合金製の熔融容器内に供給した後、これを加熱、熔融する。上記原料を完全に熔融してガラス化した後、この熔融ガラスの温度を上昇させて清澄を行う。清澄した熔融ガラスを攪拌器による攪拌によって均質化し、ガラス流出パイプに連続供給、流出し、急冷、固化してガラス成形体を得る。
The optical glass of the present invention is a glass suitable for forming a smooth optical functional surface by grinding and polishing. The suitability of cold working such as grinding and polishing, that is, cold workability is indirectly related to the glass transition temperature. A glass with a low glass transition temperature is more suitable for precision press molding than cold workability, whereas a glass with a high glass transition temperature is more suitable for cold work than precision press molding. Excellent. Therefore, in the present invention, when priority is given to cold workability, the glass transition temperature is preferably not excessively lowered, preferably higher than 630 ° C., more preferably 640 ° C. or higher, and 660 ° C. More preferably, the above is used. However, if the glass transition temperature is too high, the heating temperature at the time of reheating and softening the glass will increase, and the mold used for molding will deteriorate significantly, the annealing temperature will also become high, and the annealing furnace will Deterioration and wear are also significant. Therefore, the glass transition temperature is preferably 720 ° C. or lower, more preferably 710 ° C. or lower, and further preferably lower than 700 ° C.
(Optical glass manufacturing method)
Next, the manufacturing method of the optical glass of this invention is demonstrated. For example, a powdery compound raw material or cullet raw material is weighed and prepared in accordance with the target glass composition, supplied into a platinum alloy melting vessel, and then heated and melted. After the above raw materials are completely melted and vitrified, the temperature of the molten glass is raised to clarify. The clarified molten glass is homogenized by stirring with a stirrer, and continuously supplied to and discharged from a glass outlet pipe, rapidly cooled and solidified to obtain a glass molded body.
次に本発明のプレス成形用ガラスゴブについて説明する。
[プレス成形用ガラスコブ]
本発明のプレス成形用ガラスゴブは上記した本発明の光学ガラスからなることを特徴とする。ゴブの形状は、目的とするプレス成形品の形状に応じてプレス成形しやすい形状にする。また、ゴブの質量もプレス成形品に合わせて設定する。本発明においては、安定性の優れたガラスを使用しているので、再加熱、軟化してプレス成形してもガラスが失透しにくく、高品質の成形品を安定して生産することができる。
プレス成形用ガラスゴブの製造例は以下のとおりである。
Next, the glass gob for press molding according to the present invention will be described.
[Glass bump for press molding]
The glass gob for press molding of the present invention is characterized by comprising the above-described optical glass of the present invention. The shape of the gob is set to be easy to press according to the shape of the target press-formed product. The mass of the gob is also set according to the press-formed product. In the present invention, since glass having excellent stability is used, even if it is reheated, softened and press-molded, the glass is hardly devitrified, and a high-quality molded product can be stably produced. .
The production example of the glass gob for press molding is as follows.
第１の製造例においては、流出パイプの下方に水平に配置した鋳型にパイプから流出する熔融ガラスを連続的に鋳込み、一定の厚みを有する板状に成形する。成形されたガラスは鋳型側面に設けた開口部から水平方向へと連続して引き出される。板状ガラス成形体の引き出しはベルトコンベアによって行う。ベルトコンベアの引き出し速度を一定にしてガラス成形体の板厚が一定になるように引き出すことにより、所定の厚み、板幅のガラス成形体を得ることができる。ガラス成形体はベルトコンベアによりアニール炉内へと搬送され、徐冷される。徐冷したガラス成形体を板厚方向に切断あるいは割断し、研磨加工を施したり、バレル研磨を施してプレス成形用ガラスゴブにする。 In the first production example, the molten glass flowing out from the pipe is continuously cast into a mold horizontally disposed below the outflow pipe, and formed into a plate shape having a certain thickness. The molded glass is continuously pulled out in the horizontal direction from an opening provided on the side surface of the mold. The sheet glass molded body is pulled out by a belt conveyor. A glass molded body having a predetermined thickness and plate width can be obtained by pulling out the glass molded body so that the plate thickness of the glass molded body is constant at a constant belt conveyor drawing speed. The glass molded body is conveyed into an annealing furnace by a belt conveyor and gradually cooled. The slowly cooled glass molded body is cut or cleaved in the plate thickness direction and polished or barrel-polished to form a glass gob for press molding.
第２の製造例においては、上記鋳型の代わりに円筒状の鋳型内に熔融ガラスを鋳込んで円柱状のガラス成形体を成形する。鋳型内で成形されたガラス成形体は鋳型底部の開口部から一定の速度で鉛直下方に引き出される。引き出し速度は鋳型内での熔融ガラス液位が一定になるように行えばよい。ガラス成形体を徐冷した後、切断もしくは割断して、研磨加工またはバレル研磨を施してプレス成形用ガラスゴブとする。 In the second production example, molten glass is cast into a cylindrical mold instead of the above mold to form a columnar glass molded body. The glass molded body molded in the mold is drawn vertically downward from the opening at the bottom of the mold at a constant speed. The drawing speed may be set so that the molten glass liquid level in the mold becomes constant. After slowly cooling the glass molded body, it is cut or cleaved, and subjected to polishing or barrel polishing to obtain a glass gob for press molding.
第３の製造例においては、流出パイプの下方に円形のターンテーブルの円周上に複数個の成形型を等間隔に配置した成形機を流出パイプの下方に設置し、ターンテーブルをインデックス回転し、成形型の停留位置の一つを成形型に熔融ガラスを供給する位置（キャスト位置という）として熔融ガラスを供給し、供給した熔融ガラスをガラス成形体に成形した後、キャスト位置とは異なる所定の成形型の停留位置（テイクアウト位置）からガラス成形体を取り出す。テイクアウト位置をどの停留位置にするかは、ターンテーブルの回転速度、ガラスの冷却速度などを考慮して定めればよい。キャスト位置における成形型への熔融ガラスの供給は、流出パイプのガラス流出口から熔融ガラスを滴下し、ガラス滴を上記成形型で受ける方法、キャスト位置に停留する成形型をガラス流出口に近づけて流出する熔融ガラス流の下端部を支持し、ガラス流の途中にくびれを作り、所定のタイミングで成形型を鉛直方向に急降下することによりくびれより下の熔融ガラスを分離して成形型上に受ける方法、流出する熔融ガラス流を切断刃で切断し、分離した熔融ガラス塊をキャスト位置に停留する成形型で受ける方法などにより行うことができる。 In the third manufacturing example, a molding machine in which a plurality of molding dies are arranged at equal intervals on the circumference of a circular turntable below the outflow pipe is installed below the outflow pipe, and the turntable is index-rotated. The molten glass is supplied as a position where the molten glass is supplied to the mold (referred to as a cast position), and the supplied molten glass is formed into a glass molded body, and then is different from the cast position. The glass molded body is taken out from the stop position (takeout position) of the mold. The stop position as the take-out position may be determined in consideration of the rotation speed of the turntable, the cooling speed of the glass, and the like. The molten glass is supplied to the mold at the casting position by dropping molten glass from the glass outlet of the outflow pipe and receiving the glass droplets at the above-mentioned mold, and by bringing the molding mold retained at the casting position closer to the glass outlet. Supports the lower end of the flowing molten glass flow, creates a constriction in the middle of the glass flow, and rapidly drops the mold in the vertical direction at a predetermined timing to separate the molten glass below the constriction and receive it on the mold It can be performed by a method, a method in which the flowing molten glass flow is cut with a cutting blade, and the separated molten glass lump is received by a mold that is retained at the casting position.
成形型上でのガラスの成形は公知の方法を用いればよい。中でも成形型から上向きにガスを噴出してガラス塊に上向きの風圧を加え、ガラスを浮上させながら成形すると、ガラス成形体の表面にシワができたり、成形型との接触によってガラス成形体にカン割れが発生するのを防止することができる。 A known method may be used to form the glass on the mold. Above all, when gas is blown upward from the mold and an upward wind pressure is applied to the glass lump to form the glass while it floats, the surface of the glass mold is wrinkled, or the glass mold can be contacted with the mold by contact with the mold. It is possible to prevent cracks from occurring.
ガラス成形体の形状は、成形型形状の選択や上記ガスの噴出の仕方により、球状、回転楕円体状、回転対象軸を１つ有し、該回転対象軸の軸方向を向いた２つの面が共に外側に凸状である形状等にすることができる。これらの形状はレンズなどの光学素子あるいは光学素子ブランクをプレス成形するためのガラスゴブに好適である。このようにして得られたガラス成形体はそのまま、あるいは表面を研磨あるいはバレル研磨してプレス成形用ガラスゴブにすることができる。
[光学素子]
次に本発明の光学素子について説明する。
本発明の光学素子は、上記した本発明の光学ガラスからなることを特徴とする。本発明の光学素子は、高屈折率低分散特性を有し、Ｔａ２Ｏ５やＧｅＯ２などの高価な成分の含有量が少量またはゼロに抑えられているので、低コストにて光学的な価値の高い各種レンズ、プリズムなどの光学素子を提供することができる。
The shape of the glass molded body is spherical, spheroid, and has one rotation target axis depending on the selection of the mold shape and the gas ejection method, and two surfaces facing the axis direction of the rotation target axis. Can be formed into a shape that is convex outward. These shapes are suitable for a glass gob for press molding an optical element such as a lens or an optical element blank. The glass molded body thus obtained can be used as it is, or the surface can be polished or barrel-polished to form a glass gob for press molding.
[Optical element]
Next, the optical element of the present invention will be described.
The optical element of the present invention is characterized by comprising the above-described optical glass of the present invention. The optical element of the present invention has high refractive index and low dispersion characteristics, and the content of expensive components such as Ta 2 O 5 and GeO 2 is suppressed to a small amount or zero. Optical elements such as various high-value lenses and prisms can be provided.
レンズの例としては、レンズ面が球面または非球面である、凹メニスカスレンズ、凸メニスカスレンズ、両凸レンズ、両凹レンズ、平凸レンズ、平凹レンズなどの各種レンズを示すことができる。 Examples of the lens include various lenses such as a concave meniscus lens, a convex meniscus lens, a biconvex lens, a biconcave lens, a planoconvex lens, and a planoconcave lens having a spherical or aspheric lens surface.
こうしたレンズは、高屈折率高分散ガラス製のレンズと組み合わせることにより色収差を補正することができ、色収差補正用のレンズとして好適である。また、光学系のコンパクト化にも有効なレンズである。 Such a lens can correct chromatic aberration by combining with a lens made of high refractive index and high dispersion glass, and is suitable as a lens for correcting chromatic aberration. It is also an effective lens for making the optical system compact.
また、プリズムについては、屈折率が高いので撮像光学系に組み込むことにより、光路を曲げて所望の方向に向けることによりコンパクトで広い画角の光学系を実現することもできる。 In addition, since the prism has a high refractive index, a compact optical system with a wide angle of view can be realized by incorporating the prism into the imaging optical system and bending the optical path in a desired direction.
なお本発明の光学素子の光学機能面には、反射防止膜などの光線透過率を制御する膜を設けることもできる。
[光学素子ブランクの製造方法]
次に本発明の光学素子ブランクの製造方法について説明する。
Note that a film for controlling light transmittance such as an antireflection film may be provided on the optical functional surface of the optical element of the present invention.
[Method for manufacturing optical element blank]
Next, the manufacturing method of the optical element blank of this invention is demonstrated.
本発明の光学素子ブランクの製造方法には、以下に示す２つの態様がある。 The optical element blank manufacturing method of the present invention has the following two modes.
（第１の光学素子ブランクの製造方法）
本発明の第１の光学素子ブランクの製造方法は、研削、研磨により光学素子に仕上げられる光学素子ブランクの製造方法において、上記した本発明のプレス成形用ガラスゴブを加熱、軟化してプレス成形することを特徴とする。
(Method for manufacturing first optical element blank)
The first optical element blank manufacturing method of the present invention is a method of manufacturing an optical element blank that is finished into an optical element by grinding and polishing, and heating and softening the press molding glass gob of the present invention described above for press molding. It is characterized by.
光学素子ブランクは、目的とする光学素子の形状に、研削、研磨により除去する加工しろを加えた光学素子の形状に近似する形状を有するガラス成形体である。 The optical element blank is a glass molded body having a shape approximate to the shape of the optical element obtained by adding a processing margin to be removed by grinding and polishing to the shape of the target optical element.
光学素子ブランクを作製するにあたり、該ブランクの形状を反転した形状の成形面を有するプレス成形型を用意する。プレス成形型は上型、下型そして必要に応じて胴型を含む型部品によって構成され、上下型の成形面、あるいは胴型を使用する場合は胴型成形面を前述の形状にする。 In producing an optical element blank, a press mold having a molding surface having a shape obtained by inverting the shape of the blank is prepared. The press mold is composed of mold parts including an upper mold, a lower mold, and, if necessary, a barrel mold, and the upper and lower mold molding surfaces, or the barrel mold molding surface when the barrel mold is used, have the aforementioned shape.
次にプレス成形用ガラスゴブの表面に窒化ホウ素などの粉末状離型剤を均一に塗布し、加熱、軟化してから予熱された下型に導入し、下型と対向する上型とでプレスし、光学素子ブランクに成形する。 Next, a powder mold release agent such as boron nitride is uniformly applied to the surface of the glass gob for press molding, heated and softened, introduced into the preheated lower mold, and pressed with the upper mold facing the lower mold. Then, it is formed into an optical element blank.
次に光学素子ブランクを離型してプレス成形型から取り出し、アニール処理する。このアニール処理によってガラス内部の歪を低減し、屈折率などの光学特性が所望の値になるようにする。 Next, the optical element blank is released, removed from the press mold, and annealed. By this annealing treatment, the distortion inside the glass is reduced so that the optical characteristics such as the refractive index become a desired value.
ガラスゴブの加熱条件、プレス成形条件、プレス成形型に使用する材料などは公知のものを適用すればよい。以上の工程は大気中で行うことができる。 The glass gob heating conditions, press molding conditions, materials used for the press mold, and the like may be applied. The above steps can be performed in the atmosphere.
（第２の光学素子ブランクの製造方法）
本発明の第２の光学素子ブランクの製造方法は、研削、研磨により光学素子に仕上げられる光学素子ブランクの製造方法において、ガラス原料を熔融し、得られた熔融ガラスをプレス成形し、上記した本発明の光学ガラスからなる光学素子ブランクを作製することを特徴とする。
(Manufacturing method of the second optical element blank)
The manufacturing method of the 2nd optical element blank of this invention is a manufacturing method of the optical element blank finished to an optical element by grinding and grinding | polishing, melt | dissolves a glass raw material, press-molds the obtained molten glass, and described above An optical element blank made of the optical glass of the invention is produced.
上型、下型、必要に応じて胴型を含む型部品によりプレス成形型を構成する。前述のように光学素子ブランクの表面形状を反転した形状にプレス成形型の成形面を加工する。 A press mold is composed of mold parts including an upper mold, a lower mold, and, if necessary, a barrel mold. As described above, the molding surface of the press mold is processed into a shape obtained by inverting the surface shape of the optical element blank.
下型成形面上に窒化ホウ素などの粉末状離型剤を均一に塗布し、前述の光学ガラスの製造方法にしたがい熔融した熔融ガラスを下型成形面上に流出し、下型上の熔融ガラス量が所望の量になったところで熔融ガラス流をシアと呼ばれる切断刃で切断する。こうして下型上に熔融ガラス塊を得た後、上方に上型が待機する位置に熔融ガラス塊ごと下型を移動し、上型と下型とでガラスをプレスし、光学素子ブランクに成形する。 A powder mold release agent such as boron nitride is uniformly applied on the lower mold surface, and the molten glass melted in accordance with the optical glass manufacturing method described above flows out onto the lower mold surface, and the molten glass on the lower mold. When the amount reaches a desired amount, the molten glass stream is cut with a cutting blade called a shear. After obtaining a molten glass lump on the lower mold in this manner, the lower mold is moved together with the molten glass lump to a position where the upper mold waits upward, and the glass is pressed with the upper mold and the lower mold to form an optical element blank. .
次に光学素子ブランクを離型してプレス成形型から取り出し、アニール処理する。このアニール処理によってガラス内部の歪を低減し、屈折率などの光学特性が所望の値になるようにする。 Next, the optical element blank is released, removed from the press mold, and annealed. By this annealing treatment, the distortion inside the glass is reduced so that the optical characteristics such as the refractive index become a desired value.
ガラスゴブの加熱条件、プレス成形条件、プレス成形型に使用する材料などは公知のものを適用すればよい。以上の工程は大気中で行うことができる。 The glass gob heating conditions, press molding conditions, materials used for the press mold, and the like may be applied. The above steps can be performed in the atmosphere.
次に本発明の光学素子の製造方法について説明する。
[光学素子の製造方法]
本発明の光学素子の製造方法は、上記した本発明の方法で作製した光学素子ブランクを研削、研磨することを特徴とする。研削、研磨は公知の方法を適用することができる。
Next, the manufacturing method of the optical element of this invention is demonstrated.
[Method of manufacturing optical element]
The optical element manufacturing method of the present invention is characterized in that the optical element blank produced by the above-described method of the present invention is ground and polished. Known methods can be applied to the grinding and polishing.
次に、本発明を実施例によりさらに詳細に説明するが、本発明は、これらの例によって何等限定されるものではない。
（実施例１）
まず、表１に示す組成を有するガラスＮｏ．１〜１０が得られるように、原料として炭酸塩、硝酸塩、水酸化物、酸化物、ホウ酸などを用い、各原料粉末を秤量して十分混合し、調合原料とし、この調合原料を白金製坩堝に入れて１４００℃で加熱、熔融し、清澄、撹拌して均質な熔融ガラスした。この熔融ガラスを予熱した鋳型に流し込んで急冷し、ガラス転移温度近傍の温度で２時間保持した後、徐冷してガラスＮｏ．１〜１０の各光学ガラスを得た。いずれのガラス中にも結晶の析出は認められなかった。
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
Example 1
First, glass No. 1 having the composition shown in Table 1. In order to obtain 1-10, carbonate, nitrate, hydroxide, oxide, boric acid, etc. are used as raw materials, each raw material powder is weighed and mixed well to prepare a mixed raw material, and this mixed raw material is made of platinum. It put in the crucible, and it heated and melted at 1400 degreeC, it clarified and stirred and it was made into the homogeneous molten glass. The molten glass was poured into a preheated mold and rapidly cooled, held at a temperature in the vicinity of the glass transition temperature for 2 hours, and then gradually cooled to obtain a glass No. 1 glass. Each optical glass of 1-10 was obtained. No crystal precipitation was observed in any glass.
なお、各ガラスの特性は、以下に示す方法で測定した。測定結果を表２に示す。
・ 屈折率ｎｄおよびアッベ数νｄ
１時間あたり３０℃の降温速度で冷却した光学ガラスについて測定した。
（２）ガラス転移温度Ｔｇ
熱機械分析装置を用いて、昇温速度４℃／分の条件下で測定した。
（３）液相温度ＬＴ
ガラスを所定温度に加熱された炉内に入れて２時間保持し、冷却後、ガラス内部を１００倍の光学顕微鏡で観察し、結晶の有無から液相温度を決定した。
（４）液相温度における粘度
粘度ＪＩＳ規格 Ｚ８８０３、共軸二重円筒形回転粘度計による粘度測定方法により粘度を測定した。
（５）比重
アルキメデス法により測定した。
In addition, the characteristic of each glass was measured by the method shown below. The measurement results are shown in Table 2.
Refractive index nd and Abbe number νd
It measured about the optical glass cooled with the temperature-fall rate of 30 degreeC per hour.
(2) Glass transition temperature Tg
Using a thermomechanical analyzer, the measurement was performed under the condition of a heating rate of 4 ° C./min.
(3) Liquidus temperature LT
The glass was placed in a furnace heated to a predetermined temperature and held for 2 hours. After cooling, the inside of the glass was observed with a 100 × optical microscope, and the liquidus temperature was determined from the presence or absence of crystals.
(4) Viscosity at liquidus temperature Viscosity was measured by a viscosity measurement method using a viscosity JIS standard Z8803, a coaxial double cylindrical rotational viscometer.
(5) Specific gravity It measured by Archimedes method.
（比較例１）
特許文献１の表８、Ｎｏ．３７の組成で、Ｔａ２Ｏ５以外の成分含有量の割合を維持しつつ、Ｔａ２Ｏ５の含有量がゼロとなるように原料を調合し、加熱、熔融して得た熔融物を鋳型に流し込んで急冷した。その結果、図１の左に示すようにガラス全体が失透し、白濁してしまった。
（比較例２）
特許文献１の表８、Ｎｏ．３７の組成で、Ｔａ２Ｏ５含有量の全量を他の高屈折率付与成分であるＬａ２Ｏ３、Ｇｄ２Ｏ３、ＴｉＯ２、Ｎｂ２Ｏ５、ＷＯ３およびＺｒＯ２に均等に置換した組成に基づき原料を調合し、加熱、熔融して得た熔融物を鋳型に流し込んで急冷したところ、図１の右に示すようにガラス全体が失透し、白濁してしまった。
（実施例２）
次に実施例１のＮｏ．１〜１０の各光学ガラスからなるプレス成形用ガラスゴブを次のようにして作製した。
(Comparative Example 1)
In Table 8, No. 1 of Patent Document 1. The raw material was prepared so that the content of Ta 2 O 5 would be zero while maintaining the ratio of the content of components other than Ta 2 O 5 with the composition of 37, and the melt obtained by heating and melting the mold It was poured into and quickly cooled. As a result, as shown on the left side of FIG. 1, the entire glass was devitrified and became cloudy.
(Comparative Example 2)
In Table 8, No. 1 of Patent Document 1. With the composition of 37, the entire amount of Ta 2 O 5 content is evenly replaced with La 2 O 3 , Gd 2 O 3 , TiO 2 , Nb 2 O 5 , WO 3 and ZrO 2 which are other high refractive index imparting components The raw material was prepared based on the composition, and the melt obtained by heating and melting was poured into a mold and rapidly cooled. As a result, the entire glass was devitrified and became cloudy as shown on the right in FIG.
(Example 2)
Next, no. The glass gob for press molding which consists of each optical glass of 1-10 was produced as follows.
まず、上記各ガラスが得られるようにガラス原料を調合し、白金製坩堝に投入し、加熱、熔融し、清澄、撹拌して均質な熔融ガラスを得た。次に、熔融ガラスを流出パイプから一定流量で流出し、流出パイプの下方に水平に配置した鋳型に鋳込み、一定の厚みを有するガラス板を成形した。成形されたガラス板を鋳型側面に設けた開口部から水平方向へと連続して引き出し、ベルトコンベアにてアニール炉内へと搬送し、徐冷した。 First, glass raw materials were prepared so as to obtain the above glasses, put into a platinum crucible, heated, melted, clarified and stirred to obtain a homogeneous molten glass. Next, the molten glass was flown out from the outflow pipe at a constant flow rate and cast into a mold placed horizontally below the outflow pipe to form a glass plate having a constant thickness. The formed glass plate was continuously pulled out from the opening provided on the side surface of the mold in the horizontal direction, conveyed to the annealing furnace by a belt conveyor, and gradually cooled.
徐冷したガラス板を切断あるいは割断してガラス片を作り、これらガラス片をバレル研磨してプレス成形用ガラスゴブにした。 The slowly cooled glass plate was cut or cleaved to produce glass pieces, and these glass pieces were barrel-polished to form glass gob for press molding.
なお、流出パイプの下方に円筒状の鋳型を配置し、この鋳型内に熔融ガラスを鋳込んで円柱状ガラスに成形し、鋳型底部の開口部から一定の速度で鉛直下方に引き出した後、徐冷し、切断もしくは割断してガラス片を作り、これらガラス片をバレル研磨してプレス成形用ガラスゴブを得ることもできる。
（実施例３）
実施例２と同様に熔融ガラスを流出パイプから流出し、成形型で流出する熔融ガラス下端を受けた後、成形型を急降下し、表面張力によって熔融ガラス流を切断し、成形型上に所望の量の熔融ガラス塊を得た。そして、成形型からガスを噴出してガラスに上向きの風圧を加え、浮上させながらガラス塊に成形し、成形型から取り出してアニールした。それからガラス塊をバレル研磨してプレス成形用ガラスゴブとした。
（実施例４）
実施例３で得た各プレス成形用ガラスゴブの全表面に窒化ホウ素粉末からなる離型剤を均一に塗布した後、上記ゴブを加熱、軟化してプレス成形し、凹メニスカスレンズ、凸メニスカスレンズ、両凸レンズ、両凹レンズ、平凸レンズ、平凹レンズなどの各種レンズ、プリズムのブランクを作製した。
（実施例５）
実施例２と同様にして熔融ガラスを作り、熔融ガラスを窒化ホウ素粉末の離型剤を均一に塗布した下型成形面に供給し、下型上の熔融ガラス量が所望量になったところで熔融ガラス流を切断刃で切断した。
A cylindrical mold is disposed below the outflow pipe, molten glass is cast into the mold to form a cylindrical glass, and is drawn vertically downward from the opening at the bottom of the mold at a constant speed. Glass pieces can be obtained by cooling, cutting or cleaving to make glass pieces, and barrel-polishing these glass pieces.
(Example 3)
In the same manner as in Example 2, after the molten glass flows out from the outflow pipe and receives the lower end of the molten glass flowing out from the mold, the mold is rapidly lowered, the molten glass flow is cut by the surface tension, and the desired shape is placed on the mold. An amount of molten glass ingot was obtained. Then, gas was blown out from the mold, an upward wind pressure was applied to the glass, and the glass was molded into a glass lump while being lifted, taken out from the mold and annealed. The glass lump was then barrel-polished to form a glass gob for press molding.
Example 4
After uniformly applying a release agent composed of boron nitride powder to the entire surface of each press-molding glass gob obtained in Example 3, the gob was heated, softened and press-molded to form a concave meniscus lens, a convex meniscus lens, Various lenses such as a biconvex lens, a biconcave lens, a planoconvex lens, and a planoconcave lens, and a prism blank were prepared.
(Example 5)
In the same manner as in Example 2, a molten glass was prepared, and the molten glass was supplied to the lower mold forming surface uniformly coated with the release agent of boron nitride powder. When the amount of molten glass on the lower mold reached a desired amount, the molten glass was melted. The glass stream was cut with a cutting blade.
こうして下型上に得た熔融ガラス塊を上型と下型でプレスし、凹メニスカスレンズ、凸メニスカスレンズ、両凸レンズ、両凹レンズ、平凸レンズ、平凹レンズなどの各種レンズ、プリズムのブランクを作製した。
（実施例６）
実施例４、５で作製した各ブランクをアニールした。アニールによってガラス内部の歪を低減し、屈折率などの光学特性が所望の値になるようにする。
The molten glass block thus obtained on the lower mold was pressed with the upper mold and the lower mold, and a concave meniscus lens, a convex meniscus lens, a biconvex lens, a biconcave lens, a plano-convex lens, a plano-concave lens, etc., and a prism blank were produced. .
(Example 6)
Each blank produced in Examples 4 and 5 was annealed. Annealing reduces the internal strain of the glass so that the optical properties such as the refractive index become a desired value.
次に各ブランクを研削、研磨して凹メニスカスレンズ、凸メニスカスレンズ、両凸レンズ、両凹レンズ、平凸レンズ、平凹レンズなどの各種レンズ、プリズムを作製した。得られた光学素子の表面には反射防止膜をコートしてもよい。
（実施例７）
実施例２と同様にしてガラス板および円柱状ガラスを作製し、得られたガラス成形体をアニールして内部の歪を低減するとともに、屈折率などの光学特性が所望の値になるようした。
Next, each blank was ground and polished to prepare various lenses and prisms such as a concave meniscus lens, a convex meniscus lens, a biconvex lens, a biconcave lens, a planoconvex lens, and a planoconcave lens. The surface of the obtained optical element may be coated with an antireflection film.
(Example 7)
A glass plate and a columnar glass were produced in the same manner as in Example 2, and the obtained glass molded body was annealed to reduce internal strain and to make optical characteristics such as refractive index have desired values.
次にこれらガラス成形体を切断、研削、研磨して凹メニスカスレンズ、凸メニスカスレンズ、両凸レンズ、両凹レンズ、平凸レンズ、平凹レンズなどの各種レンズ、プリズムのブランクを作製した。得られた光学素子の表面に反射防止膜をコートしてもよい。 Next, these glass molded bodies were cut, ground, and polished to prepare concave meniscus lenses, convex meniscus lenses, biconvex lenses, biconcave lenses, planoconvex lenses, planoconcave lenses, and other lenses and prism blanks. An antireflection film may be coated on the surface of the obtained optical element.
本発明は、安定供給が可能であり、かつ優れたガラス安定性を有する高屈折率低分散性を備える光学ガラスであって、プレス成形用ガラスゴブ、光学素子ブランクおよび光学素子に好適である。 The present invention is an optical glass that can be stably supplied and has high refractive index and low dispersion having excellent glass stability, and is suitable for a glass gob for press molding, an optical element blank, and an optical element.
Claims (26)
ＳｉＯ2 ０．１〜４０％、
Ｂ2Ｏ3 １０〜５０％、
Ｌｉ2Ｏ、Ｎａ2ＯおよびＫ2Ｏを合計で０〜１０％、
ＭｇＯ、ＣａＯ、ＳｒＯおよびＢａＯを合計で０〜１０％、
ＺｎＯ ０．５〜２２％、
Ｌａ2Ｏ3 ５〜５０％、
Ｇｄ2Ｏ3 ０．１〜２５％、
Ｙ2Ｏ3 ０．１〜２０％、
Ｙｂ2Ｏ3 ０〜２０％、
ＺｒＯ2 ０〜２５％、
ＴｉＯ2 ０〜２５％、
Ｎｂ2Ｏ5 ０〜２０％、
Ｔａ2Ｏ5 ０〜７％、
ＷＯ3 ０．１％を超え２０％以下、
ＧｅＯ2 ０〜３％未満、
Ｂｉ2Ｏ3 ０〜１０％、
Ａｌ2Ｏ3 ０〜１０％、
を含み、Ｂ2Ｏ3の含有量に対するＳｉＯ2の含有量の質量比ＳｉＯ2／Ｂ2Ｏ3が１以下であり、
屈折率ｎｄが１．８６〜１．９５、アッベ数νｄが（２．３６−ｎｄ）／０．０１４以上、３８未満、かつガラス転移温度が６４０℃以上であることを特徴とする光学ガラス。 In mol%
SiO 2 0.1-40%,
B 2 O 3 10-50%,
Li 2 O, Na 2 O and K 2 O in total 0 to 10%,
MgO, CaO, SrO and BaO in total 0 to 10%,
ZnO 0.5-22%,
La 2 O 3 5-50%,
Gd 2 O 3 0.1-25%,
Y 2 O 3 0.1-20%,
Yb 2 O 3 0-20%,
ZrO 2 0-25%,
TiO 2 0-25%,
Nb 2 O 5 0-20%,
Ta 2 O 5 0~ 7%,
WO 3 exceeding 0.1% and 20% or less,
GeO 2 0 to less than 3%,
Bi 2 O 3 0-10%,
Al 2 O 3 0-10%,
Hints, B 2 O 3 mass ratio of the content of SiO 2 SiO 2 / B 2 O 3 to the content of 1 or less,
An optical glass having a refractive index nd of 1.86 to 1.95, an Abbe number νd of (2.36−nd) /0.014 or more and less than 38 , and a glass transition temperature of 640 ° C. or more .
ＬａLa 22 ＯO 3Three ５〜４５％、 5-45%,
ＧｄGd 22 ＯO 3Three ０．１〜２０％、 0.1-20%,
ＹY 22 ＯO 3Three ０．１〜１８％、および 0.1-18%, and
ＹｂYb 22 ＯO 3Three ０〜１８％ 0-18%
を含む請求項１〜８のいずれか１項に記載の光学ガラス。The optical glass according to claim 1, comprising:
請求項２２に記載のプレス成形用ガラスゴブを加熱、軟化してプレス成形することを特徴とする光学素子ブランクの製造方法。 In the method of manufacturing an optical element blank that is finished into an optical element by grinding and polishing,
A method for producing an optical element blank, comprising heating and softening the glass gob for press molding according to claim 22 to perform press molding.
ガラス原料を熔融し、得られた熔融ガラスをプレス成形し、請求項１〜２１のいずれか１項に記載の光学ガラスからなる光学素子ブランクを作製することを特徴とする光学素子ブランクの製造方法。 In the method of manufacturing an optical element blank that is finished into an optical element by grinding and polishing,
A method for producing an optical element blank, comprising melting a glass raw material, press-molding the obtained molten glass, and producing an optical element blank made of the optical glass according to any one of claims 1 to 21. .
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| JP2008019422A JP5138401B2 (en) | 2008-01-30 | 2008-01-30 | Optical glass, glass gob for press molding, optical element, manufacturing method thereof, and manufacturing method of optical element blank |
| KR1020107017010A KR101397215B1 (en) | 2008-01-30 | 2009-01-22 | Optical glass |
| CN201710928510.9A CN108328921A (en) | 2008-01-30 | 2009-01-22 | Optical glass |
| CN2009801036525A CN101932533A (en) | 2008-01-30 | 2009-01-22 | Optical glass |
| CN201410408995.5A CN104250063A (en) | 2008-01-30 | 2009-01-22 | Optical glass, glass block, optical component,optical component blank, and manufacturing method thereof |
| PCT/JP2009/051402 WO2009096439A1 (en) | 2008-01-30 | 2009-01-22 | Optical glass |
| US12/865,574 US8424344B2 (en) | 2008-01-30 | 2009-01-22 | Optical glass |
| US13/845,229 US8741795B2 (en) | 2008-01-30 | 2013-03-18 | Optical glass |
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| JP2008019422A JP5138401B2 (en) | 2008-01-30 | 2008-01-30 | Optical glass, glass gob for press molding, optical element, manufacturing method thereof, and manufacturing method of optical element blank |
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| JP2012189398A Division JP2013010688A (en) | 2012-08-30 | 2012-08-30 | Optical glass, glass gob for press-molding, optical element and method for producing the same, and method for producing optical element blank |
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| JP (1) | JP5138401B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8741795B2 (en) | 2008-01-30 | 2014-06-03 | Hoya Corporation | Optical glass |
| JP2013010688A (en) * | 2012-08-30 | 2013-01-17 | Hoya Corp | Optical glass, glass gob for press-molding, optical element and method for producing the same, and method for producing optical element blank |
| JP2013209286A (en) * | 2013-05-30 | 2013-10-10 | Hoya Corp | Optical glass, glass gob for press-forming, and optical element and method for manufacturing the same, and method for manufacturing optical element blank |
| US11319243B2 (en) | 2018-01-17 | 2022-05-03 | Corning Incorporated | High refractive index optical borate glass |
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| KR20100107030A (en) | 2010-10-04 |
| CN101932533A (en) | 2010-12-29 |
| US20110028300A1 (en) | 2011-02-03 |
| US20130210604A1 (en) | 2013-08-15 |
| JP2009179510A (en) | 2009-08-13 |
| US8424344B2 (en) | 2013-04-23 |
| KR101397215B1 (en) | 2014-05-20 |
| US8741795B2 (en) | 2014-06-03 |
| WO2009096439A1 (en) | 2009-08-06 |
| CN108328921A (en) | 2018-07-27 |
| CN104250063A (en) | 2014-12-31 |
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